TW202112534A - 蜂巢積層體及其製造方法 - Google Patents

蜂巢積層體及其製造方法 Download PDF

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Publication number
TW202112534A
TW202112534A TW109121820A TW109121820A TW202112534A TW 202112534 A TW202112534 A TW 202112534A TW 109121820 A TW109121820 A TW 109121820A TW 109121820 A TW109121820 A TW 109121820A TW 202112534 A TW202112534 A TW 202112534A
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Taiwan
Prior art keywords
honeycomb
core material
honeycomb core
porous sheet
laminate
Prior art date
Application number
TW109121820A
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English (en)
Inventor
中村優
安井達彦
Original Assignee
日商井上股份有限公司
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Publication date
Priority claimed from JP2019120769A external-priority patent/JP7218043B2/ja
Priority claimed from JP2019141300A external-priority patent/JP7356840B2/ja
Application filed by 日商井上股份有限公司 filed Critical 日商井上股份有限公司
Publication of TW202112534A publication Critical patent/TW202112534A/zh

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Abstract

本發明之蜂巢積層體係於蜂巢芯材(11)之兩面積層有表面材(21)，表面材(21)係由在碳纖維體(23)積層有多孔質片(25)而成之表面材用組件(27)含浸有熱硬化性樹脂並經硬化所構成，於多孔質片(25)與蜂巢芯材(11)的相接位置，使蜂巢芯材(11)陷入於多孔質片(25)內而由多孔質片(25)所滲出的熱硬化性樹脂呈現硬化。

Description

蜂巢積層體及其製造方法
本發明係關於一種蜂巢積層體及其製造方法。
已知一種蜂巢積層體，係於蜂巢芯材之兩面積層有表面材(含浸有熱硬化性樹脂並經硬化)。此蜂巢積層體因輕量且高剛性，故而會被用於航空器、汽車、建築等的領域。
作為蜂巢積層體之製造已知一種共硬化成形。共硬化成形會將含浸熱硬化性樹脂後之預浸體配置於蜂巢芯材的兩面，而使預浸體之熱硬化性樹脂硬化，藉此同時進行表面材之形成，以及表面材(預浸體)與蜂巢芯材的接著。
另外，蜂巢積層體會藉由預浸體之熱硬化性樹脂而於蜂巢芯材之壁的端部與表面材(預浸體)接著，被蜂巢芯材之壁所包圍之單元(cell)內的部分(中空部分)中則不與表面材接著。從而，為了提高蜂巢芯材與表面材的接著強度，將形成在蜂巢芯材之壁與表面材之間的圓角(fillet)良好地形成便會是重要的。所謂圓角是指以從表面材(預浸體)夾持蜂巢芯材之壁的端部的方式使熱硬化性樹脂隆起而形成的角。
作為將圓角良好地形成之方法，提案有一種於預浸體之熱硬化性樹脂使用黏度調整後之環氧樹脂組成物的方法(專利文獻1)。 [先前技術文獻] [專利文獻]
[專利文獻1]日本專利第4639899號公報。
[發明所欲解決之課題]
然而，於將黏度調整後之環氧樹脂組成物用於預浸體之熱硬化性樹脂而形成圓角之方法中，由於只是利用從表面材隆起的圓角來夾持蜂巢芯材之壁的端部，故而表面材與蜂巢芯材的接著強度並不高。
本發明係有鑑於前述問題點而完成之發明，其目的在於提供一種表面材與蜂巢芯材之接著強度高、且表面材難以從蜂巢芯材剝離的蜂巢積層體及其製造方法。 [用以解決課題之手段]
根據本發明一面相，提供一種蜂巢積層體，係於蜂巢芯材之兩面積層有表面材，前述表面材係由在碳纖維體積層有多孔質片而成的表面材用組件含浸有熱硬化性樹脂並經硬化所構成，前述碳纖維體係碳纖維織物或單向碳纖維片之纖維體相互積層所得，前述多孔質片與前述蜂巢芯材係相接，於前述多孔質片與前述蜂巢芯材之相接位置，前述蜂巢芯材係陷入至前述多孔質片內而由前述多孔質片所滲出之熱硬化性樹脂呈現硬化。
根據本發明一面相，提供一種蜂巢積層體，係於至少一表面具有凹凸，前述蜂巢積層體具有：蜂巢芯材；以及表面材，係積層於前述蜂巢芯材之兩面，前述表面材係含浸有使熱硬化性樹脂並經硬化所構成，於前述表面之凹陷的位置，前述蜂巢芯材係潰縮於厚度方向。
根據本發明一面相，提供一種蜂巢積層體之製造方法，前述蜂巢積層體係於蜂巢芯材之兩面積層有表面材，前述表面材係由在碳纖維體積層有多孔質片而成的表面材用組件含浸有熱硬化性樹脂並經硬化所構成，前述碳纖維體係碳纖維織物或單向碳纖維片之纖維體相互積層所得，具有下述步驟：含浸步驟，係讓前述表面材用組件含浸前述熱硬化性樹脂；積層步驟，係將含浸過前述熱硬化性樹脂的前述表面材用組件以使前述多孔質片與前述蜂巢芯材相接之方式來配置於前述蜂巢芯材之兩面而獲得壓縮加熱用積層體；以及壓縮加熱步驟，係將前述壓縮加熱用積層體進行壓縮及加熱，藉此使前述蜂巢芯材陷入至前述多孔質片，而於該陷入之部分使前述熱硬化性樹脂從前述多孔質片滲出，使該滲出之前述熱硬化性樹脂及前述表面材用組件內的前述熱硬化性樹脂硬化，來將前述表面材與前述蜂巢芯材一體化。
根據本發明一面相，提供一種蜂巢積層體之製造方法，前述蜂巢積層體係於至少一表面具有凹凸，前述蜂巢積層體具有：蜂巢芯材；以及表面材，係積層於前述蜂巢芯材之兩面，具有下述步驟：含浸步驟，係使表面材用組件含浸熱硬化性樹脂而獲得含浸完成之表面材用組件；積層步驟，係將前述含浸完成之表面材用組件配置於前述蜂巢芯材之兩面而獲得壓縮加熱用積層體；以及壓縮加熱賦形步驟，係使用於模具面具有凸部之加壓成形用模具，來將前述壓縮加熱用積層體進行壓縮及加熱，利用前述模具面之前述凸部使前述蜂巢芯材潰縮於厚度方向，以該蜂巢芯材之潰縮部分在前述壓縮加熱用積層體之表面形成凹處，而形成由該凹處之部分與相鄰之凸處之部分所構成的凹凸之形狀，使前述含浸完成之表面材用組件內的前述熱硬化性樹脂及從前述含浸完成之表面材用組件所滲出的前述熱硬化性樹脂硬化，來將前述蜂巢芯材與由前述表面材用組件所形成之前該表面材一體化。 [發明功效]
根據本發明，提供一種表面材與蜂巢芯材之接著強度高、且表面材難以從蜂巢芯材剝離的蜂巢積層體及其製造方法。
以下，關於本發明第一實施形態相關之蜂巢積層體10及其製造方法係使用圖式來加以說明。 圖1及圖2所示之蜂巢積層體10具有：蜂巢芯材11、以及積層於蜂巢芯材11的兩面而一體化之表面材21。蜂巢芯材11與表面材21係以高接著強度(表面材之剝離強度)接著著。
蜂巢芯材11具有藉由壁13而區劃出空間的複數個單元15。蜂巢芯材11的單元15之平面形狀除了由如本實施形態般之六角形(蜂巢)所構成之外，還可由四角形、三角形、五角形、八角形、凹槽形(波形)、圓形等所構成，並不限定。就蜂巢芯材11的強度及製造的容易度而言，單元之平面形狀較佳為六角形。
作為蜂巢芯材11之材質可列舉紙、金屬、樹脂、陶瓷、芳綸纖維片等，特佳為輕量性及非可燃性優異的鋁(鋁蜂巢芯材)。另外，若蜂巢芯材11之單元尺寸(網目)d過小，則蜂巢芯材11之重量便增大而使蜂巢積層體10變重，另一方面，若蜂巢芯材11之單元尺寸d過大，則會成為蜂巢積層體10之強度下降或表面材21凹陷的原因。從而，蜂巢芯材11之單元尺寸d較佳為1／32英吋至1／1英吋的範圍，更佳為1／32英吋至1／2英吋。另外，蜂巢芯材11之高度(厚度)若過小，則重量相對於體積會變重，若過高則會產生蜂巢芯材11的強度下降，故而較佳為2mm至150mm的範圍。
表面材21係由於表面材用組件27含浸有熱硬化性樹脂並經硬化之材料所構成。表面材用組件27係於碳纖維體23(由碳纖維織物或單向碳纖維片之纖維體經相互積層所得)積層有多孔質片25而形成。 為了防止凹陷等的自然變形及為了輕量性，表面材21之厚度較佳在各側為0.2mm至3.0mm。
碳纖維體23在蜂巢芯材11之各側中並不限於一層，亦可以複數層的積層(複層)來構成。 碳纖維體23在輕量及高剛性上優異。碳纖維體特佳為纖維非僅為單向的編織法所成的纖維體(織物)，例如，較佳為以縱絲與橫絲所構成的平紋編織、斜紋編織、緞紋編織及以3向絲所構成的三軸織等。另外，碳纖維體23由熱硬化性樹脂的含浸及剛性的觀點而言，纖維重量較佳為90 g／m2 至400g／m2 。碳纖維體23係碳纖維織物或單向碳纖維片之纖維體經相互積層而成，而為碳纖維織物彼此積層著的碳纖維體。另外，碳纖維體23係積層有碳纖維織物與單向碳纖維片的碳纖維體。進一步為以單向碳纖維片彼此方向的朝向成為交叉的方式來積層的碳纖維體。
多孔質片25係由發泡體或不織布所構成。在蜂巢芯材11所相接的相接位置，蜂巢芯材11會陷入至多孔質片25內。 若多孔質片25之厚度過薄，則蜂巢芯材11便無法陷入。另一方面，若多孔質片25之厚度過厚則變重，另外熱硬化性樹脂朝蜂巢芯材11之滲入便不夠充分，而使接著強度不會有效果地增大。因此，多孔質片25之厚度較佳為0.5mm至2mm。
為了能夠進行熱硬化性樹脂的含浸，作為發泡體較佳為連續氣泡構造之發泡體，例如可舉例：胺基甲酸酯樹脂發泡體或三聚氰胺樹脂發泡體。另外，由於三聚氰胺樹脂發泡體具有良好的耐燃性，故在對蜂巢積層體10要求要有耐燃性的情況下為較佳的發泡體。發泡體之密度(JIS K　7222)若過低，則使熱硬化性樹脂之含浸性及保持性變差，另一方面，若過高則蜂巢芯材便無法陷入。因此，發泡體之密度較佳為5 kg／m3 至100kg／m3 ，更佳為20 kg／m3 至80 kg／m3 。
作為不織布可舉例：碳纖維不織布、玻璃不織布、尼龍不織布、PET(polyethylene terephthalate﹔聚對苯二甲酸乙二酯)不織布等。另外，不織布之單位面積質量若過小，則含浸性及保持性便會變差，另一方面，若過大則蜂巢芯材會無法陷入，從而較佳為2g／m2 至200g／m2 。
另外，如圖2所示，在蜂巢芯材11陷入至多孔質片25內的位置係形成有圓角17。圓角17係藉由讓多孔質片25被壓縮而使熱硬化性樹脂滲出，使該滲出之熱硬化性樹脂沿著蜂巢芯材11之陷入的壁13來隆起，成為夾持著該壁13之端部的狀態而硬化所形成。
熱硬化性樹脂並不特別限定，為了提高蜂巢積層體10之剛性，需要使熱硬化性樹脂本身具有某程度之剛性，而可選自由環氧樹脂、苯酚樹脂、環氧樹脂與苯酚樹脂之混合物、胺基甲酸酯樹脂所構成之群組。另外，在對蜂巢積層體10要求要有耐燃性的情況下，熱硬化性樹脂較佳為耐燃性之樹脂。苯酚樹脂因具有良好的耐燃性而適合。熱硬化性樹脂之含浸量相對於含浸後的表面材用組件較佳為50重量％至80重量％。
蜂巢芯材11與表面材21的一體化係藉由使表面材用組件27所含有之熱硬化性樹脂在蜂巢積層體10之製造時從多孔質片25滲出而與蜂巢芯材11接觸，進而形成前述圓角17並硬化而進行。
繼而，就本發明第一實施形態相關之蜂巢積層體10之製造方法來加以說明。
本實施形態之蜂巢積層體10之製造方法係由含浸步驟、積層步驟、壓縮加熱步驟所構成。 含浸步驟中，讓於碳纖維體積層有多孔質片的表面材用組件含浸熱硬化性樹脂來製作含浸完成之表面材用組件。將含浸步驟一例顯示於下。 圖3之例中，首先如圖3之(3-1)所示，讓碳纖維體23A含浸熱硬化性樹脂F，來形成含浸完成之碳纖維體23B。碳纖維體23A及熱硬化性樹脂F係與前述蜂巢積層體10中所說明之碳纖維體及熱硬化性樹脂相同。於含浸時所使用的熱硬化性樹脂F為未硬化的液狀。
繼而如圖3之(3-2)所示，於含浸完成之碳纖維體23B的單面積層多孔質片25A，來形成含浸完成之表面材用組件27A。此時，能夠藉由附著於含浸完成之碳纖維體23B的表面的熱硬化性樹脂之黏附性(黏著性)，來將多孔質片25A貼附於含浸完成之碳纖維體23B的單面。積層於含浸完成之碳纖維體23B的多孔質片25A會含浸在與多孔質片25A接觸之含浸完成之碳纖維體23B的表面所附著之熱硬化性樹脂。多孔質片25A與蜂巢積層體10中所說明的多孔質片相同。
熱硬化性樹脂F為了易於進行含浸，較佳溶於溶劑，於含浸後，將含浸完成之表面材用組件27A以不產生熱硬化性樹脂F之硬化反應的低溫來進行乾燥，藉此去除溶劑。
含浸手段可藉由將碳纖維體23A浸漬於收納有液狀的熱硬化性樹脂F之槽的方法、藉由噴塗來將熱硬化性樹脂F噴附於碳纖維體23A的方法、藉由輥塗機來將熱硬化性樹脂F塗佈於碳纖維體23A的方法等之適當的方法來進行。
此外，於前述蜂巢積層體10中將表面材21之碳纖維體23設為複數層的情況，係藉由將前述含浸完成之碳纖維體23B積層複數片後再積層前述多孔質片25A，來形成前述含浸完成之表面材用組件27A。
前述含浸步驟亦可使碳纖維體23A與多孔質片25A分別含浸熱硬化性樹脂F後進行積層，來作為含浸完成之表面材用組件27A。另外，亦可預先於碳纖維體23A積層多孔質片25A而製作含浸前之表面材用組件，而讓該表面材用組件含浸熱硬化性樹脂來作為含浸完成之表面材用組件27A。
積層步驟中，如圖4所示，將含浸完成之表面材用組件27A配置於蜂巢芯材11A之兩面而獲得壓縮加熱用積層體10A。此時，含浸完成之表面材用組件27A係使多孔質片25A位在內側(蜂巢芯材11A側)，以多孔質片25A與蜂巢芯材11A對向接觸的方式來配置。蜂巢芯材11A係如前述蜂巢積層體10中所說明般。此外，積層操作亦可於接續進行之壓縮加熱步驟(圖5)中所使用的加壓成形機的下模具31之上面依序疊放含浸完成之表面材用組件27A、蜂巢芯材11A、含浸完成之表面材用組件27A而進行。另外，含浸完成之表面材用組件27A與蜂巢芯材11A較佳為平面尺寸為相同尺寸。
壓縮加熱步驟中，如圖5所示，將壓縮加熱用積層體10A藉由加壓成形機之下模具31與上模具33來壓縮並加熱。此外，預先改變下模具31與上模具33間的間隔而實際製造蜂巢積層體，測量所得之蜂巢積層體中的表面材之厚度來確定作為目標之表面材之厚度的下模具31與上模具33間的間隔。於壓縮加熱步驟時，下模具31與上模具33間會在適當的位置設置間隔件，使下模具31與上模具33間成為預定間隔。另外，壓縮加熱用積層體之加熱方法並不特別限定，於下模具31與上模具33設置加熱器等的加熱手段，而透過下模具31與上模具33來進行加熱是較簡單的。加熱溫度會設為熱硬化性樹脂之硬化反應溫度以上。
於壓縮加熱步驟時將壓縮加熱用積層體10A壓縮，便會使含浸完成之碳纖維體23B所含浸的熱硬化性樹脂被擠出，而含浸於與含浸完成之碳纖維體23B接觸之多孔質片25A，含浸於含浸完成之表面材用組件27A整體。此外，多孔質片25A雖在前述含浸步驟中已含浸有熱硬化性樹脂，但藉由該壓縮加熱步驟，會使多孔質片25A進一步地含浸熱硬化性樹脂。另外，藉由壓縮加熱步驟，與蜂巢芯材11A相接的多孔質片25A之部位會因蜂巢芯材11A之壁之端部而被壓縮凹陷，使蜂巢芯材11A陷入至該多孔質片25A之凹陷部位。於蜂巢芯材11A所陷入的部位，多孔質片25A內之熱硬化性樹脂會滲出，該滲出之熱硬化性樹脂會沿著蜂巢芯材11A之壁而隆起，成為夾持壁之端部的狀態。
熱硬化性樹脂會藉由加熱而開始進行硬化反應，從含浸完成之表面材用組件27A形成表面材21，而形成該表面材21與蜂巢芯材11A(11)呈一體化後的蜂巢積層體10。進而，於多孔質片25A與蜂巢芯材11A的相接位置，所滲出之熱硬化性樹脂會沿著蜂巢芯材11A之壁而隆起，在夾持住蜂巢芯材11A之壁之端部的狀態下硬化，藉此形成圓角17。之後，解除加熱壓縮而獲得蜂巢積層體10。 (實施例)
於苯酚樹脂溶液(住友電木股份有限公司製，商品名：PR-55791B，樹脂濃度60wt％乙醇溶液)中浸漬斜紋編織之碳纖維織物(帝人股份有限公司製，商品名：W-3161，纖維重量200g／m2 )，將該碳纖維織物取出而製作含浸完成之碳纖維織物。碳纖維織物係使用裁切為200mm×350mm之平面尺寸的碳纖維織物(重量14g／片)。
同樣地於各實施例及比較例製作所需片數的含浸完成之碳纖維織物，於其中各實施例所使用之各2片的含浸完成之碳纖維織物的單面，利用碳纖維織物所含浸的熱硬化性樹脂之黏附性來貼附多孔質片。
關於實施例1至實施例3及實施例5至實施例6係使用片狀之軟質胺基甲酸酯發泡體(連通氣泡構造， INOAC Corporation股份有限公司製，商品名：MF-50，厚度0.7mm，密度30kg／m3 )來作為多孔質片，而關於實施例4則使用碳不織布(阿波製紙公司製，商品名：CARMIX　CFRP，厚度1mm，單位面積重量120g／m2 )來作為多孔質片。 此外，關於比較例用之含浸完成之碳纖維織物並未貼附多孔質片。
之後，將貼附有多孔質片之含浸完成之碳纖維織物與未貼附多孔質片之含浸完成之碳纖維織物在25℃之室溫下自然乾燥2小時，進一步在60℃的氛圍下乾燥1小時，而製作具多孔質片之預浸體與無多孔質片之預浸體。
作為蜂巢芯材係於各實施例及比較例分別使用裁切為200mm×350mm之平面尺寸之單元尺寸1／8英吋的鋁蜂巢(厚度3mm，重量37g／片)、單元尺寸1英吋之鋁蜂巢(厚度3mm，重量40g)、以及單元尺寸1／8英吋之鋁蜂巢(厚度2mm、重量25g)。
繼而，於預先將離型劑塗佈於表面的SUS(Stainless Steel；不鏽鋼)製的下模具之上，就各實施例來依序疊放配置：無多孔質片之預浸體達所需片數、具多孔質片之預浸體、鋁蜂巢、具多孔質片之預浸體、無多孔質片之預浸體達所需片數。此時，多孔質片會與鋁蜂巢相接。藉此，以蜂巢芯材與預浸體之多孔質片相接之方式將由預浸體配置於蜂巢芯材之兩面而構成之壓縮加熱用積層體設置於下模具之上。無多孔質片之預浸體與具多孔質片之預浸體的積層體係相當於含浸完成之表面材用組件。此外，關於比較例，係將依序疊放配置有無多孔質片之預浸體達所需片數、鋁蜂巢、無多孔質片之預浸體達所需片數而構成之壓縮加熱用積層體設置於下模具。
於加壓成形機之下模具的四個角落配置厚度對應於各實施例及比較例之蜂巢積層體的厚度的SUS製間隔件，將下模具之上的壓縮加熱用積層體在150℃以上模具(平板狀)來抵壓30分鐘，來進行壓縮及加熱，使苯酚樹脂反應硬化。此時之壓縮加熱用積層體的加熱係藉由安裝於加壓成形用下模具與上模具型的熔鑄加熱器來進行。此外，就實施例1至實施例2、實施例4至實施例6及比較例係施加10MPa之面壓(加壓壓力)而以上模具(平板狀)來抵壓以進行壓縮及加熱；另一方面，就實施例3係施加15MPa之面壓(加壓壓力)而以上模具(平板狀)來抵壓以進行壓縮及加熱。
之後，將下模具與上模具在室溫進行冷卻後，開啟下模具與上模具，獲得蜂巢積層體。所得之各實施例的蜂巢積層體係由無多孔質之預浸體與具多孔質片之預浸體而成的積層體(含浸完成之表面材用組件)經硬化而成的表面材積層於鋁蜂巢之兩面而一體化後的蜂巢積層體。該各實施例之蜂巢積層體中，鋁蜂巢會陷入至多孔質片，而該陷入位置會形成有圓角。另一方面，比較例之蜂巢積層體係複數片的無多孔質之預浸體所積層並經硬化而成的表面材積層於鋁蜂巢之兩面而一體化後的蜂巢積層體，蜂巢芯材並無陷入，並未形成有圓角。
另外，對各實施例及比較例之蜂巢積層體進行表面材之彎曲彈性係數之測定。測定結果會在彎曲彈性係數為20MPa以上且蜂巢積層體未剝離的情況評價為「〇」，除此之外的情況(彎曲彈性係數未達20MPa或／及蜂巢積層體有剝離的情況)則評價為「×」。 彎曲彈性係數之測定係基於JIS K 7074來進行。
將各實施例及比較例之構成與評價顯示於表1。實施例1至實施例6之蜂巢積層體的任一者彎曲彈性係數均為25GPa至31GPa且表面材無剝離，評價為「〇」。實施例1至實施例6之蜂巢積層體因著使蜂巢芯材陷入至表面材之多孔質片所達成的接著強度增大與圓角所達成之接著強度增大這兩方面而成為表面材之剝離強度高且剛性高之蜂巢積層體。 [表1]
  碳纖維織物之總片數 多孔質片 蜂巢積層體之厚度(mm) 蜂巢芯材之厚度(mm) 蜂巢芯材之單元尺寸(in) 加壓壓力(MPa) 表面材剝離 (有無) 彎曲彈性係數(GPa) 評價
實施例1 4 胺基甲酸酯樹脂發泡體 4.0 3 1／8 10 無 27 〇
實施例2 6 胺基甲酸酯樹脂發泡體 4.5 3 1／8 10 無 31 〇
實施例3 6 胺基甲酸酯樹脂發泡體 4.5 3 1／8 15 無 31 〇
實施例4 6 碳不織布 4.5 3 1／8 10 無 30 〇
實施例5 6 胺基甲酸酯樹脂發泡體 4.5 3 1 10 無 26 〇
實施例6 4 胺基甲酸酯樹脂發泡體 3.0 2 1／8 10 無 25 〇
比較例 4 - 4.0 3 1／8 10 有 6 ×
另一方面，比較例之蜂巢積層體係彎曲彈性係數為6GPa，而評價為「×」。比較例之蜂巢積層體僅使表面材(預浸體)相接於蜂巢芯材而硬化，蜂巢芯材並無朝表面材陷入，亦未形成有圓角，從而相較於各實施例，表面材之接著強度會較低而表面材容易剝離且剛性大幅低落。
如此般，根據本發明，便能夠獲得使蜂巢芯材陷入至積層於蜂巢芯材之兩面的表面材之多孔質片而形成有圓角的蜂巢積層體，故而能夠藉由蜂巢芯材之陷入所得之接著強度增大效果與利用圓角所得之接著強度增大的兩者效果，來將蜂巢芯材與表面材強固(表面材之剝離強度大)地接著的蜂巢積層體。
進而，本發明之蜂巢積層體10之製造方法中，毋須預先形成表面材而使該表面材以接著劑來與蜂巢芯材接著。亦即，本發明之蜂巢積層體10之製造方法中，於使預浸體之熱硬化性樹脂硬化時，便能夠同時進行表面材(預浸體)之形成與蜂巢芯材之接著，而能夠使製造步驟合理化。
[第二實施形態] 繼而，作為本發明之第二實施形態，係使用圖6至圖10來說明於表面具有凹118及凸119之蜂巢積層體110及其製造方法。關於與上述第一實施形態同樣的構造及製造方法會省略其說明。 另外，於以往的表面設置有凹凸之蜂巢積層體會需要預先於蜂巢芯材之表面形成凹凸，而有使製造成本提高之問題。進而，於形成有凹凸之蜂巢芯材之表面積層表面材時，會有表面材在蜂巢芯材之凹凸的位置浮起，而無法正確地將表面材積層於蜂巢芯材之虞。
另外，於將黏度調整後之環氧樹脂組成物用於預浸體之熱硬化性樹脂而形成圓角的方法中，由於僅是利用從表面材之內面(背面)隆起之圓角來夾持蜂巢芯材之壁之端部，故而接著強度並不高。
本發明之第二實施形態有鑑於前述問題點而完成之形態，提供一種係無需預先於蜂巢芯材之表面形成凹凸，而能夠在表面材與蜂巢芯材的積層一體化的同時，於蜂巢芯材形成凹凸而於積層體之表面設置凹凸的蜂巢積層體及其製造方法。
如圖6及圖7所示，第二實施形態之蜂巢積層體110係於表面具有凹118及凸119。蜂巢積層體110具有：蜂巢芯材111，以及積層於蜂巢芯材111之兩面而一體化的表面材121。於蜂巢積層體110之表面形成有凹118與凸119，來提高蜂巢芯材111與表面材121之接著強度(表面材的剝離強度)。 此外，凸119為相鄰於凹118的部分，藉由於表面形成有凹118，相鄰於凹118之部分便會相對性地變高而形成凸119。
本實施形態之蜂巢芯材111係使位在表面之凹118的部分之壁113A(參照圖7)成為於蜂巢芯材111之厚度(高度)方向上受到壓縮而呈潰縮的狀態。 蜂巢芯材111之單元尺寸(網目)d若過小，則蜂巢芯材111之重量便增大而變重，或是難以使蜂巢芯材潰縮於厚度方向，而難以形成凹118及凸119。另一方面，蜂巢芯材111之單元尺寸(網目)d若過大，則會成為蜂巢積層體110之強度低落或表面材121凹陷的原因。因此，蜂巢芯材111之單元尺寸(網目)d較佳為1／32英吋至1／1英吋的範圍，更佳為1／32英吋至1／2英吋。
表面材121、碳纖維體123、多孔質片125、圓角117之構造及素材係與上述第一實施形態相同。另外，發泡體或不織布之素材、熱硬化性樹脂所使用之樹脂的種類等亦與上述第一實施形態相同。
繼而，就本發明第二實施形態相關之於表面具有凹118及凸119之蜂巢積層體110之製造方法來加以說明。 本實施形態之蜂巢積層體110之製造方法係由含浸步驟、積層步驟、壓縮加熱賦形步驟所構成。 圖8之(8-1)及(8-2)所示的含浸步驟係與上述第一實施形態之含浸步驟相同。含浸步驟中，使得於碳纖維體123B積層有多孔質片125A之表面材用組件127含浸熱硬化性樹脂F而製作含浸完成之表面材用組件127A。
圖9所示之積層步驟亦與上述第一實施形態之積層步驟相同。如圖9所示，將含浸完成之表面材用組件127A配置於蜂巢芯材111A之兩面，獲得壓縮加熱用積層體110A。
壓縮加熱賦形步驟中，如圖10所示，將壓縮加熱用積層體110A藉由加壓成形機之下模具131與上模具133來壓縮並加熱。於上模具133之模具面(加壓面)設置有用以形塑出蜂巢積層體110之凹118的凸部135。凸部135具有對應於凹118之形狀，並設置在對應於凹118之位置。凸部135之高度(相對於模具面之突出量)係小於蜂巢積層體110之厚度，較佳為小於蜂巢芯材111A之厚度。
利用加壓成型機所達成之壓縮加熱用積層體110A的壓縮程度會以使蜂巢積層體110中之表面材121之厚度成為0.2mm至表面材121之厚度(非壓縮狀態)的方式來進行壓縮。此外，預先改變下模具131與上模具133間的間隔而實際製造蜂巢積層體110，測量所得之蜂巢積層體110中的表面材121之厚度來確定作為目標之表面材121之厚度的下模具131與上模具133間的間隔。於壓縮加熱賦形步驟時，下模具131與上模具133間會在適當的位置設置間隔件，使下模具131與上模具133間成為預定間隔。另外，壓縮加熱用積層體之加熱方法並不特別限定，於下模具131與上模具133設置加熱器等的加熱手段，而透過下模具131與上模具133來進行加熱是較簡單的。加熱溫度會設為熱硬化性樹脂之硬化反應溫度以上。
於壓縮加熱賦形步驟時若壓縮加熱用積層體110A受到壓縮，便會使含浸完成之碳纖維體123B所含浸的熱硬化性樹脂被擠出，而含浸於與含浸完成之碳纖維體123B接觸之多孔質片125A，含浸於含浸完成之表面材用組件127A整體。此外，多孔質片125A雖在前述含浸步驟中已含浸有熱硬化性樹脂，但藉由該壓縮加熱賦形步驟，會使多孔質片125A進一步地含浸熱硬化性樹脂。另外，藉由壓縮加熱賦形步驟，多孔質片125A中之與蜂巢芯材111A相接的部位會因蜂巢芯材111A之壁之端部而被壓縮凹陷，使蜂巢芯材111A陷入至凹陷部位。於蜂巢芯材111A所陷入的部位中，多孔質片125A內之熱硬化性樹脂會滲出，該滲出之熱硬化性樹脂會沿著蜂巢芯材111A之壁而隆起，成為夾持壁之端部的狀態。
另外，壓縮加熱用積層體110A由上模具133之凸部135所壓縮之部分中，蜂巢芯材111之壁會於厚度方向受到壓潰而於壓縮加熱用積層體110A之表面形成凹處。
熱硬化性樹脂會藉由加熱而開始進行硬化反應，藉由熱硬化性樹脂之硬化從含浸完成之表面材用組件127A形成表面材121，使該表面材121與蜂巢芯材111A(11)接著而一體化，來形成於表面具有凹118及凸119之蜂巢積層體110。另外，於多孔質片125A與蜂巢芯材111之相接位置，所滲出之熱硬化性樹脂會沿著前述蜂巢芯材111A之壁來隆起，而在夾持蜂巢芯材111A之壁之端部的狀態下使熱硬化性樹脂硬化。藉此來形成圓角117。之後，解除加熱壓縮，獲得於表面具有凹118及凸119之蜂巢積層體110。表面之凹118及凸119係由上模具133之凸部135所賦形出的凹118之部分以及和凹118相鄰且相對性地成為凸處之凸119之部分所構成。
此外，上述實施形態之說明中，雖顯示讓蜂巢芯材陷入至多孔質片之例，但亦可不設置多孔質片，不讓蜂巢芯材陷入至多孔質片而於蜂巢積層體之表面設置凹凸。 另外，第二實施形態中，雖顯示將複數平行的凹形成於表面的情況，但亦可將凹處形成為井字狀或成為圓形或波形等的曲線狀。進而，雖顯示僅於蜂巢積層體之單面設置凹凸之例，但亦可於蜂巢積層體之兩面設置凹凸。於此情況，係在加壓成形機之下模具之模具面與上模具之模具面兩者設置用以形成凹部之凸部。 另外，亦可讓蜂巢芯材之壁部潰縮之程度產生部分差異，藉由讓設置於蜂巢積層體之表面的凹部之深度產生部分差異，來形成凹部之深度有所差異的凹凸。在此情況，加壓成形用機之上模具及下模具之模具面的用以形成凹部之凸部係部分性地改變高度。 (實施例)
於苯酚樹脂溶液(住友電木股份有限公司製，商品名：PR-55791B，樹脂濃度60wt％乙醇溶液)中浸漬斜紋編織之碳纖維織物(帝人股份有限公司製，商品名：W-3161，纖維重量200g／m2 )，將該碳纖維織物取出而製作含浸完成之碳纖維織物(碳纖維體)。碳纖維織物(碳纖維體)係使用裁切為200mm×350mm之平面尺寸的碳纖維織物(重量14g／片)。
同樣地製作所需片數之含浸完成之碳纖維織物(碳纖維體)，這些當中，於實施例1所使用之2片的含浸完成之碳纖維織物的單面利用碳纖維織物所含浸之熱硬化性樹脂的黏附性來貼附多孔質片。此外，並未於實施例2所使用之含浸完成之碳纖維織物貼附多孔質片。
作為多孔質片，係使用片狀之軟質胺基甲酸酯發泡體(連通氣泡構造， INOAC Corporation股份有限公司製，商品名：MF-50，厚度0.7mm，密度30kg／m3 )。
之後，將貼附有多孔質片之含浸完成之碳纖維織物與未貼附多孔質片之含浸完成之碳纖維織物在25℃之室溫下自然乾燥2小時，進而在60℃氛圍下乾燥1小時，而製作具多孔質片之預浸體與無多孔質片之預浸體。
作為蜂巢芯材係將單元尺寸1／8英吋之鋁蜂巢(昭和飛行器股份有限公司製，商品名：AL-1／8-5052-.001，厚度3mm，重量37g／片)裁切為200mm×350mm的平面尺寸來加以使用。
關於實施例1，係於預先將離型劑塗佈於表面的SUS製的加壓成形機的下模具之上依序疊放配置：2片之無多孔質片之預浸體、1片具多孔質片之預浸體、蜂巢芯材、1片具多孔質片之預浸體、2片無多孔質片之預浸體。此時多孔質片會與蜂巢芯材相接。藉此，將以使蜂巢芯材與預浸體之多孔質片會相接之方式來將預浸體配置於蜂巢芯材之兩面而構成之壓縮加熱用積層體設置於加壓成形機之下模具之上。此外，無多孔質片之預浸體與具多孔質片之預浸體的積層體係相當於含浸完成之表面材用組件。
另一方面，關於實施例2，係於預先將離型劑塗佈於表面的SUS製之下模具之上依序疊放配置：2片無多孔質片之預浸體2枚、蜂巢芯材、2片無多孔質片之預浸體。此外，無多孔質片之預浸體的積層體係相當於含浸完成之表面材用組件。
實施例1及實施例2中，於下模具之四個角落配置有厚度對應於各實施例所製作之積層體之厚度的SUS製間隔件(實施例1中為4.5mm，實施例2中為4.0mm)。另外，將下模具之上所配置的壓縮加熱用積層體以模具面設置有井字狀之凸部(凹部形成用之凸部)的上模具來抵壓。如此般，藉由下模具及上模具來對壓縮加熱用積層體進行壓縮及加熱，使苯酚樹脂反應硬化。各凸部之寬度為1mm，深度為3mm，凸部之間隔為100mm。壓縮及加熱係在150℃施加10MPa面壓而進行30分鐘。此時之壓縮加熱用積層體的加熱係藉由安裝於下模具與上模具的熔鑄加熱器來進行。
之後，讓下模具與上模具在室溫進行冷卻後，開啟下模具與上模具，獲得於表面具有凹118及凸119之蜂巢積層體。如此般所形成之凹118及凸119係由以上模具之井字狀凸部所壓縮而形成之井字狀的凹部與相鄰於凹部之部分(凹部間之部分)所構成。 另外，於使用具多孔質片之預浸體之實施例1中，使鋁蜂巢陷入至具多孔質片之預浸體的多孔質片，而在該陷入位置明確地形成有圓角。 另一方面，於未使用具多孔質片之預浸體的實施例2中，係使得無多孔質片之預浸體與鋁蜂巢相接而使熱硬化性樹脂硬化，於相接部幾乎未形成有圓角。
如此般，根據本實施形態，便能夠在表面材與蜂巢芯材之積層及一體化的同時，於蜂巢積層體之表面設置凹118及凸119。 進而，藉由採用讓蜂巢芯材陷入至表面材之多孔質片，從多孔質片所滲出之熱硬化性樹脂產生硬化之構成，可將圓角良好地形成，使蜂巢芯材與表面材之接著強度(剝離強度)成為良好。
本申請係基於2019年6月28日所申請之日本專利申請案(日本特願2019-120769)及2019年7月31日所申請之日本專利申請案(日本特願2019-141300)的申請，該內容係作為參照而被援用於此。 [產業可利用性]
根據本發明，能夠提供一種表面材與蜂巢芯材之接著強度高、且表面材難以從蜂巢芯材剝離之蜂巢積層體及其製造方法。
10,110:蜂巢積層體 10A:壓縮加熱用積層體 11,11A,111,111A:蜂巢芯材 13:壁 15:單元 17:圓角 21,121:表面材 23,23A,23B,123,123B:碳纖維體 25,25A,125,125A:多孔質片 27,27A,127,127A:表面材用組件 31,131:下模具 33,135:上模具 113A:壁 117:圓角 118:凹 119:凸 d:單元尺寸 F:熱硬化性樹脂
[圖1]係將本發明第一實施形態中的蜂巢積層體一部分切除顯示之平面圖。 [圖2]係圖1之2-2截面圖。 [圖3]係顯示本發明第一實施形態的製造方法中之含浸步驟之圖。 [圖4]係顯示本發明第一實施形態的製造方法中之積層步驟之圖。 [圖5]係顯示本發明第一實施形態的製造方法中之加熱壓縮步驟之圖。 [圖6]係將本發明第二實施形態中的蜂巢積層體一部分切除顯示之平面圖。 [圖7]係圖6之XIII-XIII線中之截面圖。 [圖8]係顯示本發明第二實施形態中之製造方法的含浸步驟之圖。 [圖9]係顯示本發明第二實施形態中之製造方法的積層步驟之圖。 [圖10] 顯示本發明之第二實施形態中之製造方法的加熱壓縮步驟之圖。
10:蜂巢積層體
11:蜂巢芯材
13:壁
15:單元
17:圓角
21:表面材
23:碳纖維體
25:多孔質片
27:表面材用組件

Claims (16)

  1. 一種蜂巢積層體，係於蜂巢芯材之兩面積層有表面材； 前述表面材係由在碳纖維體積層有多孔質片而成的表面材用組件含浸有熱硬化性樹脂並經硬化所構成，前述碳纖維體係碳纖維織物或單向碳纖維片之纖維體相互積層所得； 前述多孔質片與前述蜂巢芯材相接； 於前述多孔質片與前述蜂巢芯材之相接位置，前述蜂巢芯材係陷入至前述多孔質片內而由前述多孔質片所滲出之熱硬化性樹脂呈現硬化。
  2. 一種蜂巢積層體，係於至少一表面具有凹凸； 前述蜂巢積層體具有：蜂巢芯材；以及表面材，係積層於前述蜂巢芯材之兩面； 前述表面材係含浸有熱硬化性樹脂並經硬化所構成； 於前述表面之凹的位置，前述蜂巢芯材係潰縮於厚度方向。
  3. 如請求項2所記載之蜂巢積層體，其中前述蜂巢芯材由鋁蜂巢所構成。
  4. 如請求項3所記載之蜂巢積層體，其中前述表面材係由在碳纖維體積層有多孔質片而成的表面材用組件含浸有熱硬化性樹脂並經硬化所構成，前述碳纖維體係碳纖維織物或單向碳纖維片之纖維體相互積層所得； 前述多孔質片與前述蜂巢芯材係相接； 於前述多孔質片與前述蜂巢芯材之相接位置，前述蜂巢芯材係陷入於前述多孔質片內而由前述多孔質片所滲出的熱硬化性樹脂呈現硬化。
  5. 如請求項1或4所記載之蜂巢積層體，其中前述多孔質片之厚度為0.5mm至2mm。
  6. 如請求項1或4所記載之蜂巢積層體，其中前述多孔質片由發泡體或不織布所構成。
  7. 如請求項6所記載之蜂巢積層體，其中前述發泡體之密度為5 kg／m3 至100kg／m3 ，或前述不織布之單位面積重量為2g／m2 至200g／m2 。
  8. 如請求項1至4中任一項所記載之蜂巢積層體，其中前述蜂巢芯材之單元尺寸為1／32英吋至1／1英吋。
  9. 一種蜂巢積層體之製造方法，前述蜂巢積層體係於蜂巢芯材之兩面積層有表面材； 前述表面材係由在碳纖維體積層有多孔質片而成的表面材用組件含浸有熱硬化性樹脂並經硬化所構成，前述碳纖維體係碳纖維織物或單向碳纖維片之纖維體相互積層所得； 具有下述步驟： 含浸步驟，係讓前述表面材用組件含浸前述熱硬化性樹脂； 積層步驟，係將含浸過前述熱硬化性樹脂的前述表面材用組件以使前述多孔質片與前述蜂巢芯材相接之方式來配置於前述蜂巢芯材之兩面而獲得壓縮加熱用積層體；以及 壓縮加熱步驟，係將前述壓縮加熱用積層體進行壓縮及加熱，藉此使前述蜂巢芯材陷入至前述多孔質片，而於該陷入之部分使前述熱硬化性樹脂從前述多孔質片滲出，使該滲出之前述熱硬化性樹脂及前述表面材用組件內的前述熱硬化性樹脂硬化，來將前述表面材與前述蜂巢芯材一體化。
  10. 一種蜂巢積層體之製造方法，前述蜂巢積層體係於至少一表面具有凹凸； 前述蜂巢積層體具有：蜂巢芯材；以及表面材，係積層於前述蜂巢芯材之兩面； 具有下述步驟： 含浸步驟，係使表面材用組件含浸熱硬化性樹脂而獲得含浸完成之表面材用組件； 積層步驟，係將前述含浸完成之表面材用組件配置於前述蜂巢芯材之兩面而獲得壓縮加熱用積層體；以及 壓縮加熱賦形步驟，係使用於模具面具有凸部之加壓成形用模具，來將前述壓縮加熱用積層體進行壓縮及加熱，以利用前述模具面之前述凸部使前述蜂巢芯材潰縮於厚度方向，以該蜂巢芯材之潰縮部分在前述壓縮加熱用積層體之表面形成凹處，而形成由該凹處之部分與相鄰之凸處之部分所構成的凹凸之形狀，使前述含浸完成之表面材用組件內的前述熱硬化性樹脂及從前述含浸完成之表面材用組件所滲出的前述熱硬化性樹脂硬化，來將前述蜂巢芯材與由前述表面材用組件所形成之前述表面材一體化。
  11. 如請求項10所記載之蜂巢積層體之製造方法，其中前述蜂巢芯材由鋁蜂巢所構成。
  12. 如請求項10所記載之蜂巢積層體之製造方法，其中前述表面材用組件係由在碳纖維體積層有多孔質片所構成，前述碳纖維體係碳纖維織物或單向碳纖維片之纖維體相互積層所得； 前述積層步驟係將前述含浸完成之表面材用組件以前述多孔質片與前述蜂巢芯材相接之方式來配置於前述蜂巢芯材之兩面而形成壓縮加熱用積層體； 前述壓縮加熱賦形步驟係利用前述模具面之前述凸部使前述蜂巢芯材潰縮於厚度方向，藉此讓前述蜂巢芯材陷入至前述多孔質片，以該陷入之部分使前述熱硬化性樹脂從前述多孔質片滲出，使該滲出之前述熱硬化性樹脂及前述表面材用組件內之前述熱硬化性樹脂硬化，來將前述蜂巢芯材與由前述含浸完成之表面材用組件所形成的前述表面材一體化。
  13. 如請求項9或12所記載之蜂巢積層體之製造方法，其中前述多孔質片之厚度為0.5mm至2mm。
  14. 如請求項9或12所記載之蜂巢積層體之製造方法，其中前述多孔質片由發泡體或不織布所構成。
  15. 如請求項14所記載之蜂巢積層體之製造方法，其中前述發泡體之密度為5kg／m3 至100kg／m3 ，或前述不織布之單位面積重量為2g／m2 至200g／m2 。
  16. 如請求項9至12中任一項所記載之蜂巢積層體之製造方法，其中前述蜂巢芯材之單元尺寸為1／32英吋至1／1英吋。
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